WO2009123969A2 - Polymères anti-inflammables dérivés de désoxybenzoïne - Google Patents

Polymères anti-inflammables dérivés de désoxybenzoïne Download PDF

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WO2009123969A2
WO2009123969A2 PCT/US2009/038789 US2009038789W WO2009123969A2 WO 2009123969 A2 WO2009123969 A2 WO 2009123969A2 US 2009038789 W US2009038789 W US 2009038789W WO 2009123969 A2 WO2009123969 A2 WO 2009123969A2
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Prior art keywords
polymer
substituted
hydrogen
bedb
deoxybenzoin
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PCT/US2009/038789
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English (en)
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WO2009123969A3 (fr
Inventor
Todd Emrick
E. Bryan Coughlin
Thangamani Ranganathan
Michael Beaulieu
Richard Farris
Bon-Cheol Ku
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University Of Massachusetts
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Priority to US12/934,386 priority Critical patent/US8314202B2/en
Publication of WO2009123969A2 publication Critical patent/WO2009123969A2/fr
Publication of WO2009123969A3 publication Critical patent/WO2009123969A3/fr
Priority to US13/655,123 priority patent/US9175131B2/en
Priority to US14/859,336 priority patent/US9822205B2/en
Priority to US14/859,338 priority patent/US9340635B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the invention relates to flame retardant polymers. More particularly, the invention relates to deoxybenzoin-derived polymers, and related methods and uses thereof.
  • Polymers are a mainstay of modern society, for example, widely used in fabricating textiles, upholstery, construction materials, various air, land or sea vehicles, and microelectronic devices and appliances.
  • the inherent flammability of many polymers poses a significant threat, especially in enclosed or isolated spaces. Therefore, as synthetic polymers are used extensively in society as plastics, rubbers, and textiles, polymer flammability has been recognized as a safety hazard and remains an important challenge in polymer research.
  • Fire or flame retardant (FR) additives may be used to temper polymer flammability.
  • brominated organic compounds comprise a large subset of FRs used today.
  • Flame retardants are incorporated into polymer materials as small molecule additives, or as part of the polymer backbone, to reduce flammability.
  • a number of halogenated molecules, including aromatic and aliphatic brominated compounds, have been employed to reduce polymer flammability. Brominated aromatic flame retardants can be found in a wide-range of products, including computer, textiles, foam furniture, and construction materials.
  • FR compounds also face legislative scrutiny due to health and environmental concerns, particularly related to bioaccumulation ⁇ e.g., polybrominated diphenyl ether (PBDE) has been detected in umbilical cord serum and breast milk).
  • PBDE polybrominated diphenyl ether
  • the environmental accumulation of haligenated flame retardants raises concerns that are restricting their use, and requires the development of nonhalogenated alternatives.
  • halogenated flame retardants release hydrogen halide gas upon combustion, which is especially undesirable in confined spaces, such as on aircrafts and ships.
  • non-halogenated flame retardant additives such as alumina trihydrate, compromise the physical and mechanical properties of polymers when loaded at high levels.
  • the invention is based in part on the unexpected discovery of certain novel deoxybenzoin-derived polymers and compositions thereof are unique and possess desirable flame or fire retardant properties.
  • Such unique polymers which have deoxybenzoin-based backbone or side chains, along with methods for their syntheses and uses thereof have been discovered and are expect to have broad impact on such diverse fields of fabricating textiles, upholstery, construction materials, various air, land or sea vehicles, and microelectronic devices and appliances.
  • These novel polymers address some of the most urgent needs for anti-flammable polymeric materials with much better environmental impact profile than many conventional polymers.
  • the present invention generally relates to novel dexoybenzoin-derived polymers having a structural repeating unit having the structure of:
  • each of Ri and R 2 is independently selected from hydrogen, un-substituted or substituted alkyl, aryl, -O-alkyl, -O-aryl groups; each of Xi, X 2 , and X 3 is independently O, -N(R)-, single bond, or -O-R 4 -; wherein R is hydrogen or an alkyl group, R 4 is an unsubstituted or substituted alkylene or arylene; and
  • R 3 is selected from an alkylene, arylene, -C(O)-, -R 5 -C(O)-R 5 -, -Si(R 6 )(R 7 )-, -R 8 - S(O) 2 -R 8 -, and -C(O)-X 4 -R 9 -X 5 -C(O)- groups; each ofR 5 , R 8 , and R 9 is an unsubstituted or substituted alkylene or arylene; each Rg and R 7 is independently selected from hydrogen, un-substituted or substituted alkyl groups; and
  • X 4 and X 5 is independently O, -N(H)-, or a single bond.
  • each of Rj and R 2 is hydrogen.
  • each of Xi and X 2 is O.
  • ach of Ri and R 2 is hydrogen, X 3 is O, and R 3 is -C(O)-.
  • each of Xi and X 2 is -N(H)-.
  • X 3 is a single bond.
  • the polymers of the invention may be a co-polymer.
  • the polymer may be cured with a di- or multi-functional amine.
  • the polymer may be cured with a di- or multifunctional carboxylic acid.
  • the present invention generally relates to polymers comprising a structural repeating unit having the structure of:
  • each of Ri, R 2 , R 3 and R 4 is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups, provided that at least one of Ri, R 2 , R 3 and R 4 comprises a deoxybenzoin moiety having the structure of:
  • each of Ri, R 2 , and R 3 is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups and R 4 is
  • X is a unsubstituted or substituted bivalent alkyl or aryl group
  • R 5 is a hydrogen, substituted or un-substituted alkyl or aryl groups.
  • the polymer may be a co-polymer, for example, further comprises a structural repeating unit having the structure of
  • Ri', R 2 ', R 3 ' and R 4 ' is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups.
  • the polymer includes a structural repeating unit having the structure of:
  • the polymer may include a structural repeating unit having the structure of:
  • R is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups
  • R 6 is a -OH, or substituted or un-substituted alkyl groups.
  • the polymer may include a structural repeating unit having the structure of:
  • each of Ri', R 2 ', and R 3 ' is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups, and R 6 ' is one or more of -OH, or substituted or un- substituted alkyl groups.
  • Copolymers of the invention include random copolymers, statistical copolymer, block copolymers, graft-block copolymers, star-shaped copolymers, etc.
  • the present invention also encompasses composite materials that comprises a polymer of the invention.
  • the present invention also encompasses a polymer resin of the polymer of the invention, wherein the polymer resin has heat release capacity (HRC) of less than 200 J/g-K, preferably less than 150 J/g-K, more preferably less than 100 J/g-K.
  • HRC heat release capacity
  • a polymer resin of the polymer may have a char yield of between 20% to 40%, between 25% and 35%, between 30% and 40% and more than 40%.
  • the invention further encompasses a product comprising a deoxybenzoin-derived polymer of the invention.
  • the deoxybenzoin moiety may be found in the backbone or in the pendant side chain of the polymer.
  • FIG. Al shows certain exemplary deoxybenzoin-containing polymers.
  • FIG. Bl shows certain exemplary TGA thermograms of BEDB resin.
  • FIG. B2 shows certain exemplary lap shear strength measurement of certain BEDB- based resins.
  • FIG. B3 shows certain exemplary plot of storage modulus and tan ⁇ versus temperature certain BEDB-based resins.
  • FIG. Cl shows certain exemplary polyurethane foam formulations and flammability data.
  • FIG. Dl shows certain exemplary test specimens.
  • Certain compounds of the present invention may exist in particular geometric or stereoisomeric forms.
  • the present invention contemplates all such compounds, including cis- and trans -isomers, R- and S-enantiomers, diastereomers, (D)-isomers, (L)-isomers, the racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention.
  • Additional asymmetric carbon atoms may be present in a substituent such as an alkyl group. All such isomers, as well as mixtures thereof, are intended to be included in this invention.
  • protecting group By the term “protecting group”, as used herein, it is meant that a particular functional moiety, e.g., O, S, or N, is temporarily blocked so that a reaction can be carried out selectively at another reactive site in a multifunctional compound.
  • a protecting group reacts selectively in good yield to give a protected substrate that is stable to the projected reactions; the protecting group should be selectively removable in good yield by readily available, preferably non-toxic reagents that do not attack the other functional groups; the protecting group forms an easily separable derivative (more preferably without the generation of new stereogenic centers); and the protecting group has a minimum of additional functionality to avoid further sites of reaction.
  • Oxygen, sulfur, nitrogen, and carbon protecting groups may be utilized. Examples of a variety of protecting groups can be found in Protective Groups in Organic Synthesis, Third Ed. Greene, T.W. and Wuts, P. G., Eds., John Wiley & Sons, New York: 1999.
  • alkyl refers to a saturated linear or branched (including cyclic) hydrocarbon free radical, unsubstituted (i.e., with corresponding number of carbon and hydrogen atoms), or optionally substituted with substituents known to those skilled in the art.
  • alkyl groups include (Ci-C 6 ) alkyl (or Ci-C 6 alkyl), which refers to a saturated linear or branched free radical consisting essentially of 1 to 6 carbon atoms (i.e., 1, 2, 3, 4, 5, or 6 carbon atoms) and a corresponding number of hydrogen atoms.
  • Exemplary (C 1 -C 6 ) alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.
  • Other (Ci-C 6 ) alkyl groups will be readily apparent to those of skill in the art given the benefit of the present disclosure.
  • aryl and heteroaryl refer to stable mono- or polycyclic, heterocyclic, polycyclic, and polyheterocyclic unsaturated moieties having preferably 3-14 carbon atoms, each of which may be substituted or unsubstituted.
  • Substituents include, but are not limited to, any of the previously mentioned substitutents, i.e., the substituents recited for aliphatic moieties, or for other moieties as disclosed herein, resulting in the formation of a stable compound.
  • aryl refers to a mono- or bicyclic carbocyclic ring system having one or two aromatic rings including, but not limited to, phenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, and the like.
  • heteroaryl refers to a cyclic aromatic radical having from five to ten ring atoms of which one ring atom is selected from S, O, and N; zero, one, or two ring atoms are additional heteroatoms independently selected from S, O, and N; and the remaining ring atoms are carbon, the radical being joined to the rest of the molecule via any of the ring atoms, such as, for example, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl,oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, and the like.
  • Novel deoxybenzoin-derived polymers and compositions thereof that possess desirable flame or fire retardant properties have been unexpectedly discovered.
  • Such unique polymers, which have deoxybenzoin-based backbone or side chains, are expect to have broad impact and address some of the most urgent needs for anti-flammable polymeric materials with much better environmental impact profile than many conventional polymers.
  • Low-flammable polymers are desired that are halogen- free and possess high thermal stability, low heat of combustion, and a low combustion hear release capacity (HRC), with minimal release of toxic fumes.
  • Intrinsically fire-resistant polymers that undergo significant carbonization upon heating are highly desirable, as carbonaceous char formation effectively averts combustion by producing an insulating layer on the polymer surface. Such char formation may also be realized from composite materials in which an additive assists in generating the desired char.
  • PCFC Pyrolysis combustion flow calorimetry
  • HRC defined as the maximum amount of heat released per unit mass per degree Kelvin (J/g-K), is viewed as an inherent material property and a reliable predictor of polymer flammability. HRC values obtained by PCFC, across a range of many polymer types, are found to scale with the larger, conventional bench-scale flammability experiments.
  • Aromatic polyesters prepared from bisphenols and phthalic acids are examples of high performance engineering thermoplastics.
  • Conventional bisphenol A (BPA)-based polyacrylates are widely used, but exhibit higher-than-desired flammability (e.g., BPA- polyarylates have HRC ⁇ 400 J/g-K).
  • Polyarylates containing l,l-dichloro-2,2-bis(4- hydroxyphenyl)ethylene bisphenol C, or BPC
  • BPC-based polymers are transparent and processable, and exhibit excellent mechanical and dielectric properties.
  • BPC-based polymers are well within the "ultra fire-resistant" category (HRC ⁇ 100 J/g-K). With BPC-based polymers, the evolution of hydrogen chloride gas at elevated temperatures, is concerning and may limit ultimate scale-up and manufacturing efforts.
  • BPC derivatives can be converted into the corresponding diphenylacetylene by loss of the chlorines, followed by phenyl migration.
  • this rearrangement mechanism leads to char formation, and the presence of halogen serves primarily to setup this rearrangement.
  • diphenylacetylene-containing poly(arylether ketone)s showed heat release characteristics of similar magnitude to the corresponding BPC- versions.
  • these alkyne-containing aromatic polymers are prone to side-reactions and crosslinking even at moderately high temperatures, and have less-than-optimal processability and mechanical properties typically desired in polymer materials.
  • a deoxybenzoin moiety e.g., 4,4'-bishydroxydeoxybenzoin (BHDB)
  • BHDB 4,4'-bishydroxydeoxybenzoin
  • Polymers derived from BHDB exhibit low combustion heat release rates and total heat of combustion.
  • the desirable heat release properties associated with DHBD-containing polymers are believed to arise from the thermally-induced conversion of BHDB to diphenylacetylene moieties that char by aromatization. (See, Ellzey, et al, Macromolecules 2006, 39, 3553).
  • BHDB 4,4'-bishydroxydeoxybenzoin
  • BPA-based polymers while not nearly as flammable as polyethylene or polystyrene, are moderately flammable and thus used in conjunction with FR additives.
  • Bisphenol C (BPC)- based polymers are attractive for their charring decomposition that insulates the polymer-air interface, and precludes the evolution of gaseous decomposition products required for sustained combustion.
  • a general concern over the chlorine content of BPC has slowed (or precluded) commercialization of BPC-containing polymers.
  • the present invention generally relates to novel dexoybenzoin-derived polymers having a structural repeating unit having the structure of:
  • each of R] and R 2 is independently selected from hydrogen, un-substituted or substituted alkyl, aryl, -O-alkyl, -O-aryl groups; each of Xi, X 2 , and X 3 is independently O, -N(R)-, single bond, or -O-R 4 -; wherein R is hydrogen or an alkyl group, R 4 is an unsubstituted or substituted alkylene or arylene; and
  • R 3 is selected from an alkylene, arylene, -C(O)-, -R 5 -C(O)-R 5 -, -Si(R 6 )(R 7 )-, -R 8 - S(O) 2 -R 8 -, and -C(O)-X 4 -R 9 -X 5 -C(O)- groups; each of R 5 , Rg, and R 9 is an unsubstituted or substituted alkylene or arylene; each R 6 and R 7 is independently selected from hydrogen, un-substituted or substituted alkyl groups; and
  • X 4 and X 5 is independently O, -N(H)-, or a single bond.
  • each of R] and R 2 is hydrogen.
  • each of Xi and X 2 is O.
  • ach of Ri and R 2 is hydrogen, X 3 is O, and R 3 is -C(O)-.
  • each of Xi and X 2 is -N(H)-. In certain other embodiments, X 3 is a single bond.
  • the polymers of the invention 1 may be a co-polymer.
  • the polymer may be cured with a di- or multi-functional amine.
  • the polymer may be cured with a di- or multifunctional carboxylic acid.
  • poly(ether ketone)s can be prepared by the polycondensation of t-butyldimethylsilyl (TBDMS)- protected BHDB with 4,4'-difluorobenzophenone using cesium fluoride catalyst in N- methylpyrrolidone solvent at 150 0 C.
  • polysulfones can be prepared by the condensation of BHDB with 4,4'- dichlorodiphenyl sulfone using a base as catalyst.
  • Polyphosphates can be synthesized either by interfacial or solution polymerization of BHDB with phenyl dichlorophosphate, and polyethers can be prepared by the reaction of BHDB with 1 ,4-dibromobenzene using a basic catalyst such as potassium carbonate.
  • Corresponding polysiloxanes can be synthesized by condensing BHDB with disubsituted dichlorosilanes (aliphatic or aromatic).
  • Polycarbonates can be prepared by one of several methods, including: (a) interfacial polycondensation of BHDB with phosgene or triphosgene; (b) solution polycondensation of BHDB with phosgene or triphosgene; and (c) melt polymerization of BHDB with diphenyl carbonate.
  • a synthetic strategy for synthesizing deoxybenzoin ⁇ based polycarbonates is provided in Scheme Al.
  • a series of copolycarbonates containing BPA and BHDB were prepared by solution polycondensation using phosgene while varying the molar ratios of the two bisphenols.
  • the polymerization uses triethylamine as base, 4-dimethylaminopyridine as catalyst, and 4-t-butylphenol as end-capping agent in anhydrous dichloromethane. Extraction of the reaction mixture with dichloromethane, followed by a washing with water, and precipitation into methanol afforded the polymers as white fibrous solids.
  • the polycarbonates prepared (e.g., including without limitation, the random copolymers of Scheme Al) in this fashion were soluble in many organic solvents, including chloroform, dichloromethane, THF, DMF and DMSO, whereas the BHDB-polycarbonate was sparingly soluble in most of these solvents, but gave good solubility in DMF and DMSO.
  • PCFC was employed to measure the flammability characteristics such as heat release capacity (HRC) and total heat release (THR) for the polycarbonates.
  • HRC heat release capacity
  • THR total heat release
  • the BPA- polycarbonate exhibited HRC of -400 J/g-K, which indicates its modest flammability properties (Table Al).
  • PET poly(ethylene terephalate)
  • PET-like substitutes Various types of low flammability aromatic polyesters (PET-like substitutes) can be envisioned using deoxybenzoin, as shown in Scheme A2.
  • the deoxybenzoin unit is inserted into the aromatic polyester structure; in the second method, a terephathaloyl unit was replaced by deoxybenzoin moiety; and in the final strategy, the same was done but with a reversed connectivities.
  • R aliphatic or aromatic groups
  • standard polyurethane conditions may be used, such as bibutyltindilaurate catalysis, and N,N-dimethylformamide or N-methylpyrolidone as solvent.
  • R group of diamine or diol a variety of polyurethanes can be obtained. If the R group is aliphatic spacer, then it leads to flexible polyurethanes, whereas use of aromatic groups result in rigid polyurethanes.
  • Aliphatic spacers of various lengths can be incorporated into the BHDB moiety in order to increase the flexibility as well as increasing the nucleophilicity of hydroxyl groups.
  • One such example is shown in Scheme A4.
  • the present invention generally relates to polymers comprising a structural repeating unit having the structure of:
  • each of Ri, R 2 , R 3 and R 4 is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups, provided that at least one of Rj, R 2 , R 3 and R 4 comprises a deoxybenzoin moiety having the structure of:
  • each of Ri, R 2 , and R 3 is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups and R 4 is
  • X is a unsubstituted or substituted bivalent alkyl or aryl group
  • R 5 is a hydrogen, substituted or un-substituted alkyl or aryl groups.
  • the polymer may be a co-polymer, for example, further comprises a structural repeating unit having the structure of
  • the polymer includes a structural repeating unit having the structure of:
  • Ri, R 2 , R 3 , and R 5 is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups.
  • the polymer may include a structural repeating unit having the structure of:
  • each of Ri, R 2 , R 3 , and R 5 is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups, and R 6 is a -OH, or substituted or un-substituted alkyl groups.
  • the polymer may include a structural repeating unit having the structure of:
  • each of Ri', R 2 ', and R3' is independently selected from hydrogen, un-substituted or substituted alkyl, and aryl groups, and R 6 ' is one or more of -OH, or substituted or un- substituted alkyl groups.
  • the copolymer of the invention may include a structural repeating unit selected from methylmethacrylate, acrylonitrile, budadiene, ethylene, isoprene, or derivatives thereof.
  • Chain-growth polymers such as polystyrene (PS) and poly(m ethyl methacrylate) (PMMA), are commodity polymers with numerous current commercial uses. These polymers possess high flammability levels, as reflected in their heat release capacity (HRC) values measured by pyrolysis combustion flow calorimetry (consider, e.g., HRC values of 930 J/g-K for polystyrene and 510 J/g-K for PMMA).
  • HRC heat release capacity
  • Polyolefins and various other chain-growth polymers comprising deoxybenzoin pendant groups can include, without limitation, corresponding random, block, statistical, segmented, graft, graft-block and star-shaped copolymers.
  • Representative, non-limiting examples include copolymers of styrene, methylmethacrylate, acrylonitrile, butadiene, ethylene, isoprene, and with acrylonitrile and butadiene (to give ABS terpolymers).
  • Copolymers of the invention include random copolymer, statistical copolymers, block copolymers, graph-block copolymers, star-shaped copolymers, etc.
  • the present invention also encompasses composite materials that comprises a polymer of the invention.
  • the composite material may further comprising a flame-retarding additive.
  • the present invention also encompasses a polymer resin of the polymer of the invention, wherein the polymer resin has heat release capacity (HRC) of less than 200 J/g-K, preferably less than 150 J/g-K, more preferably less than 100 J/g-K.
  • HRC heat release capacity
  • a polymer resin of the polymer may have a char yield of between 20% to 40%, between 25% and 35%, between 30% and 40% and more than 40%.
  • the invention further encompasses a product comprising a deoxybenzoin-derived polymer of the invention.
  • the deoxybenzoin moiety may be found in the backbone or in the pendant side chain of the polymer.
  • a product may include a polymer having a polyethylene or a polystyrene backbone and deoxybenzoin-containing side chains.
  • the polymer has a M w of greater than 10,000, preferably greater than 50,000, and more preferably greater than 100,000.
  • BEDB diepoxide (or diglycidyl ether) of BHDB
  • BEDB meaning bisepoxydeoxybenzoin
  • BEDB a novel epoxy compound
  • BEDB resins though halogen-free, have HRC values that approach the halogenated versions, and that are significantly lower than conventional non-halogenated versions.
  • Various epoxy formulations were prepared and tested. In case of the epoxy resins cured with aromatic amines, the BEDB based resins had lower T g than those based on BPA.
  • the char residues of the BEDB resins (30-35 %) were much higher than those of the EBPA resins (12-16 %) and ETBBA resins (23-24 %), and the HRC of the EBHDB resins were lower than those of the EBPA resins.
  • the mixed amine with the same mole fraction of 4,4'-DDS and 4,4'-DDM was used as curing agent, the cured resin based on BEDB exhibited lower HRC than those cured a single amine.
  • the brominated epoxy materials gave moderately lower HRC values relative to the BEDB materials.
  • CT Compact tension
  • the specimens were pre-cracked with a Leco VC-50 diamond saw and a razor blade, and tested at a crosshead speed of 0.5 mm/min on an Instron 4411 equipped with a 0.1 kN (10 kg) load cell.
  • the value of the crack length/width (a/W) of specimens is approximately 0.5.
  • Three to five specimens of each resin formulation were tested at room temperature. Lap shear testing was carried out following ASTM D 1002. Lap shear specimens having a bond area of 12.7 mm were made using two 2024-T3 aluminum panels.
  • Bond line thickness was controlled by the inclusion of short lengths of 0.127 mm diameter wire. Tests were conducted at a crosshead speed of 50 mm/min on an Instron tensile test machine. For reproducibility, three-to-five specimens of each formulation were tested (each at room temperature).
  • BHDB 4,4'-bishydroxydeoxybenzoin
  • 4,4 -Bishydroxydeoxybenzoin (BHDB) was prepared by demethylation of desoxyanisoin, according to the literature.
  • Desoxyanisoin (50 g, 195.1 mmol) and pyridine hydrochloride (90.2 g, 780.5 mmol) were added to a round-bottom flask equipped with a condenser. The mixture was refluxed for 5 h at 200 0 C, cooled to room temperature, and poured into water.
  • ETBBA diepoxide (diglycidyl ether) of 3,3 ,5,5 -tetrabromobisphenol A (ETBBA)
  • ETBBA diepoxide (diglycidyl ether) of 3,3 ,5,5 -tetrabromobisphenol A
  • Samples for TGA, PCFC, and DMA were prepared by mixing the diepoxides with a stoichiometric equivalent of curing agent at 60-130 0 C. The homogeneous mixtures were cured for 2 hours at 130-180 0 C, followed by a 2 hour post-cure at 180-200 0 C in a Teflon mold. Mixing and curing temperatures were optimized by considering the glass transition temperature and gelation rate of each formulation.
  • BEDB the diepoxide (or diglycidyl ether) of BHDB
  • BEDB was prepared by reacting BHDB with epichlorohydrin under basic conditions, as shown in Scheme Bl.
  • BEDB was obtained as a white solid in 80% yield, with a distinctly higher melting point (125-130 0 C) than the BPA version (43-47 0 C).
  • Nuclear magnetic resonance (NMR) spectroscopy confirmed the intended structure, as seen for example in the proton spectrum showing a singlet at 4.17 ppm for the methylene group adjacent to the ketone, and characteristic glycidyl ether resonances at 4.25, 3.95, and 2.76 ppm.
  • BEDB was then used as the electrophilic difunctional monomer in curing reactions with multifunctional nucleophiles, including 4,4'- diaminodiphenyl sulfone (4,4'-DDS), 4,4'-diaminodiphenyl methane (4,4'-DDM), and meta- phenylene diamine (m-PDA).
  • BEDB, EBPA, and ETBBA epoxy formulations were prepared using 4,4'-DDS, 4,4'-DDM, and mPDA as the curing agents (Table Bl).
  • Homogeneous formulations were prepared by mixing the liquid-phase epoxides with the amines at 60-130 0 C. In the DSC instrument, the mixtures were heated to fully cure the formulation ⁇ i.e., when no further increase in the heat of reaction was seen), and the reported glass transition temperatures were taken from the second heating curves of the fully cured samples (following quenching with liquid nitrogen). Several interesting characteristics were noted in the cured resins.
  • the BEDB-based resins consistently gave the lowest T g values, which might be due to the absence of the steric bulk between the phenyl groups of BPA and TBBA.
  • those cured with DDS had the highest T g values, possibly due to a combination of the polarity and rigidity of the sulfonyl groups in the DD S -containing networks.
  • the initial degradation temperatures (T d O the formulations were near or above the mid-300 0 C range. It is known that the presence of bromine reduces the thermal stability of amine-cured epoxy resins, and TBBA resins specifically are destabilized by formation of HBr, and instability of the cyclohexadienone structure produced the initial step of thermal decomposition. (See, Lo et al. J Polym Sci: Polym Chem Ed 1984; 22: 1707-1715; Luda et al. Polym Degrad Stabil 2007; 92: 1088-1100.)
  • PCFC Pyrolysis combustion flow calorimetry
  • THR total heat release
  • HRC heat release capacity
  • T max the sample temperature at maximum heat release rate. While an ideal predictor of flammability would be the heat release rate, this depends on the sample heating rate, making quantification difficult. HRC eliminates this uncertainty, more reliably predicting polymer flammability as an inherent material property).
  • PCFC is now recognized as a convenient analytical tool for analyzing small scale (milligram) samples of combustible materials.
  • BEDB-based resins are quite promising materials.
  • the BEDB/m-PDA revealed a HRC of 390 J/(g K), approximately half of that obtained for conventional EBPA/m-PDA resin (HRC of 760 J/(g K)).
  • Char yields of the BEDB-based epoxies were at least twice that of the BPA versions, increasing from about 12% for BPA-based adhesives to 25-30% for BEDB-based resins.
  • the BEDB- and TBBA-based resins showed much lower HRC and THR relative to the BPA-based resins.
  • Halogen-containing polymers usually produce high levels of incomplete combustion products, and non-combustible gas, which contribute to gas phase combustion inhibition.
  • the BEDB-based resins exhibit significantly lower HRC and THR than those of the BPA resins. This is because that the effective char formation at the molecular level is to reduce the amount of combustible products and gases.
  • FIG. Bl shows TGA thermograms of BEDB resins cured with 4,4'-DDS, 4,4'- DDM, and a mixture of 4,4'-DDS and 4,4 ' -DDM.
  • the derivative weight curve of the resin cured with mixed amines is broader and its maximum value is smaller than those of the resins cured with a single amine. Because HRC is directly proportional to dW/dT and the heat of combustion, this reduction in the maximum value of derivative weight can reduce HRC.
  • amine formulations were prepared for BEDB and EBPA. The results for the formulations are listed in Table B2.
  • the T g increased with the mole fraction of 4,4'-DDS
  • the char residue increased with the mole fraction of 4,4'-DDM.
  • the HRC of the BPA based resin is roughly dependant on the mole fraction of 4,4'-DDS, and is the lowest (454 ⁇ 30 J/(g K)) at 0.8 mole fraction of 4,4'-DDS.
  • the resins cured with the same mole fraction of 4,4'-DDS and 4,4'-DDM has the lowest HRC (321 ⁇ 10 J/(g K)).
  • BEDB/4,4'-DDS 181 30 420 ⁇ 14 17.2 ⁇ 0.2
  • Subscripts mean mole fraction of compounds.
  • b T g S were obtained from DSC.
  • c Char residues were obtained from TGA at 850 0 C in nitrogen (heating rate 10 0 C /min).
  • the adhesion strength of cured epoxy resins are derived from several elements, including the hydroxyl groups generated during the curing, the functionality of the components used, and the chemical structures of particular epoxide and curing agent. (See, Pham et al. Encyclopedia of Chemical Technology, vol. 10, New York: Wiley, 2004. pp. 347- 461.) Lap shear, a characteristic test of bonding shear strength, is indicative of adhesive environmental durability.
  • Cross-link density typically related to the average molecular weight between crosslinks (MW C ), is an important factor governing the physical properties of cured resins. According to rubber elasticity theory, the cross-link density of a thermoset resin is proportional to the modulus in the rubbery plateau region. (See, Katz et al. Polymer 1963; 4: 417-421; Lesser et al. J Appl Polym Sci 1997; 66: 387-395.)
  • FIG. B3 plots storage modulus and tan ⁇ versus temperature for EBPA/4,4'-DDS, BEDB/4,4'-DDS, EBPA/4,4'-DDM, and BEDB/4,4'-DDM, and the results are listed in Table B3.
  • the moduli of BEDB-based epoxy resins at T g + 40 0 C are higher than those of EBPAs. Therefore, the cross-link densities of the BEDB resins are higher than for the EBPA case, while T g values of the EBPA resins are -5-13 0 C higher than those of BEDB resins. In each case, a second run gave data identical to the first, such that no further curing was needed.
  • BEDB was used to prepare epoxy formulations with ortho-, meta-, andp ⁇ r ⁇ -aromatic diamines which have methyl groups, chlorides, and methoxy groups in different positions.
  • Formulations and thermal properties of epoxy resins with prepared with these different diamines are listed in Table B5.
  • resins cured with substituted diamines gave higher T g values than those prepared using non-substituted r ⁇ et ⁇ -phenylene diamine (mPDA). This is explained by the more restricted segmental motions of the cured resins possessing the methyl groups and chlorides in a densely cross- linked system.
  • T d i Initial degradation temperatures (T d i) of the resins are mid-300 0 C range, except for BEDB/4-CmP resin. Unlike other formulations which have a very short interval between Td max and T d , ( ⁇ T d ), BEDB/4-CmP and BEDB/3,3 '-DMoB exhibited values of 37 and 22 for ⁇ T d , respectively. This high ⁇ T d might be related to increasing the flame-retardancy of the resin while exhibiting the same total heat release (THR).
  • the resins cured with chlorinated diamines showed relatively low HRCs, also shown in Table B6. This reduction of HRC can be explained by gas phase combustion inhibition.
  • BEDB/ort/zo-diaminophenylchloide systems exhibited higher HRC and THR than resins cured with chlorinated meto-aromatic diamines.
  • the methyl substituted diaminobenzene, BEDB/2,3-diamino toluene had the lowest value of HRC, but much higher THR than those of the resins cured with met ⁇ -diaminobenzenes.
  • substituted meta-system provides an opportunity for higher flame-retardancy than the ortho- case, likely due to more facile intermolecular cyclization reactions during thermal decomposition.
  • Resins cured with substituted biphenyls exhibited higher char residues and flame-retardancy than those cured with DDM, DDS, and mPDA.
  • the resin cured with methoxy substituted biphenyl gave HRC and THR significantly lower than the resin cured with the /wet ⁇ -diaminophenylchloride.
  • Polyurethanes an important class of thermoplastics, are synthesized by the polymerization of diisocyanates (or polyisocyanates) with diols (or polyols) in presence of a catalyst.
  • Polyurethane formulations used today cover an extensive range of hardness and densities.
  • a variety of polyurethanes can be obtained in the form of foams (rigid or flexible), rubbers, elastomers, coatings or adhesives.
  • Low density flexible polyurethane foams are used in upholstery and bedding, while low density rigid foams are employed as thermal insulation and in automobile dashboards.
  • Gel pads and print rollers utilize soft solid polyurethane elastomers, while hard solid plastics are useful in structural parts.
  • Polyurethanes belong to reactive processing polymers, in which reactive monomers and oligomers are processed, neat or in solution.
  • the reactive components are processed as liquids for the manufacture of polyurethane foams and elastomers.
  • Reaction injection molding (RIM) technology illustrates in a unique way the reactive processing of liquid polyurethane components, i.e.
  • RIM combines the processing of liquids and the forming of thermoset parts in a more economical process than injection molding.
  • FR additives are required for most polyurethane products, especially flexible foams used in upholstery and mattresses. FR additives impede the progress of fire and reduce the amount of heat and smoke released. Halogenated FR additives are useful, cost-effective, and provide improved fire safety of polyurethanes.
  • halogenated FR additives are useful, cost-effective, and provide improved fire safety of polyurethanes.
  • PBDEs polybrominated diphenyl ethers
  • a proactive solution towards elimination of toxic halogenated FR additives would be to embed intrinsic anti-flammable characteristics into the polymer.
  • Another aspect of the invention addresses the problem of polyurethane flammability by the synthesis of deoxybenzoin diisocyanate (DBDI) and its use in the preparation of polyurethanes.
  • DBDI deoxybenzoin diisocyanate
  • the utility of DBDI is demonstrated by synthesizing polyurethanes with two different diols.
  • the thermal properties of these deoxybenzoin-containing polyurethanes were measured and compared to those of conventional polyurethanes synthesized from commercially available diisocyanates, such as 4,4'-methyldiphenyl diisocyanate (MDI) and 2,4-toluene diisocyanate (TDI).
  • MDI 4,4'-methyldiphenyl diisocyanate
  • TDI 2,4-toluene diisocyanate
  • FT-IR spectroscopy indicated characteristic absorption bands at 2267 and 1747 cm “1 (isocyanate group) and 1664 cm “ (CO stretching of deoxybenzoin).
  • H NMR spectroscopy showed a singlet for the methylene group at 3.99 ppm, and four multiplets for the aromatic protons at 6.60, 6.67, 6.99 and 7.83 ppm.
  • the carbonyl and methylene carbon resonances of deoxybenzoin appeared at 196 and 43.7 ppm, respectively. The two isocyanate carbons were found at 124.2 and 124.7 ppm.
  • High resolution mass spectrometry (HRMS) indicated molecular ion peak at 278.0684 (calculated 278.0691).
  • Diisocyanate 5 was then used in polymerization chemistry with various diols to afford polyurethanes.
  • 4,4'- bishydroxydeoxybenzoin (BHDB) was used as a diol in an A 2 + B 2 polymerization with DBDI.
  • This attempted polymerization gave only oligomers despite exploring a variety of reaction conditions, including various mole percent of dibutyltin dilaurate, different solvents (NMP, DMSO, and DMF), temperatures from 90-150 0 C, and reaction times up to 48 hours. None of the conditions that were tried could compensate for the low reactivity of phenols towards aromatic diisocyanates.
  • Deoxybenzoin-rich polyurethanes were prepared by first extending BHDB to an aliphatic diol, as shown in Scheme C2. BHDB was heated with ethylene carbonate at 180 0 C (neat melt) with sodium carbonate as catalyst 27 to afford 6 in excellent yield (94%) and high purity. 1 H NMR spectroscopy indicated a downfield shift for the methylene proton of deoxybenzoin to 4.20 ppm (4.11 ppm in BHDB). The protons of the ethylene units were seen at 3.72, 3.82, 3.94, and 4.07 ppm, while the hydroxyl protons resonate at 4.84 and 4.91 ppm.
  • the protons of the ethylene spacers resonate as triplets at 3.69, 3.73, 3.93 and 4.06 ppm.
  • the urethane NH protons were found at 8.58 and 9.75 ppm as broad singlets and the aromatic protons were in the region of 6.9-8.0 pm with expected integration ratios.
  • FT-IR spectrum showed typical urethane absorption bands at 3322 cm “ (N-H stretching) and 1714 cm “1 (CO stretching) alonj with the carbonyl stretching band of deoxybenzoin unit at 1672 cm "1 .
  • the molecular structural characterization was done by FT-IR and 1 H NMR spectroscopy.
  • the polyurethane 13 prepared from DBDI and 1,3-propanediol
  • FT-IR the polyurethane 13
  • the carbonyl stretching of deoxybenzoin unit was found at 1675 cm "1 .
  • Proton-NMR spectroscopy revealed peaks at 2.06 (multiplet, 2H) and 4.16 ppm (triplet, 4H) for the propanediol component, while the methylene protons of deoxybenzoin resonate at 4.21 ppm as singlet.
  • the aromatic protons are found as four multiplets at 7.14, 7.35, 7.66, and 7.99 ppm, each accounting for two protons.
  • the urethane NH protons were found as broad singlets at 9.61 and 10.1 ppm.
  • PCFC pyrolysis combustion flow calorimetry
  • TGA thermogravimetric analysis
  • DSC differential scanning calorimetry
  • HRC heat release capacity
  • THR total heat release
  • HRC is the peak heat release rate normalized to the heating rate
  • THR is defined as the heat of complete combustion of the pyrolysis gases per unit initial mass of a material.
  • HRC is an inherent material property and hence a good predictor of the flammability of polymers.
  • TGA provides the onset of decomposition temperatures along with char residues, while glass transition temperatures (T g ) are obtained by DSC (Table C2).
  • 1,3 -propanediol as the diol component possess high flammability characteristics as seen from their large HRC (-350-550 J/g-K) and THR ( ⁇ 22 kJ/g) values.
  • Replacement of MDI or TDI with DBDI in these polyurethane systems reduces HRC and THR to 140 J/g-K and 13 kJ/g, respectively.
  • Substitution of aliphatic diol (12) with a deoxybenzoin-containing diol (6) in MDI or TDI-based polyurethanes converts them from highly flammable into moderately flammable with a reduced HRC (-250 J/g-K) and THR (-17 kJ/g).
  • DSC studies demonstrated the amorphous nature of all the polyurethanes, as seen from the observation of only glass transition temperature (T g ) when the heating cycle was carried out up to 250 0 C.
  • T g glass transition temperature
  • DBDI-based polyurethane exhibited T g of 156 °C
  • MDI and TDI-based polyurethanes showed relatively lower temperatures of 110 and 119 0 C, respectively.
  • a typical industrial process of polyurethane foam synthesis involves the reaction of polymeric diisocyanates (eg. MDI or TDI-based prepolymer) with a polyol (polyether or polyester-based) using a foaming agent (eg. water) and an amine or organometallics-based catalyst.
  • a foaming agent eg. water
  • an amine or organometallics-based catalyst e.g. water
  • Rigid or flexible foams are obtained by varying the nature, functionality, and molecular weight of polyols employed. Addition of chain extenders and cross linkers (low molecular weight hydroxyl and amine terminated compounds) also play an important role in determining the final morphology of polyurethane foams as fibers, elastomers or adhesives.
  • BHDB was reacted with ditosyl protected 1,3 -propanediol using potassium carbonate as base in acetone to obtain the oligomer containing tosyl end groups (16) in 65% yield.
  • the product was characterized by 1 H NMR spectroscopy.
  • the methylene protons of the deoxybenzoin unit changed from a clear singlet at 4.1 ppm to several singlet peaks in the region of 3.8-4.0 ppm indicating the formation of oligomer.
  • the two methylene protons connected to oxygen atoms of the spacer resonate at 4.15-4.22 ppm as broad peaks.
  • Polyurethane foams were then synthesized by the reaction of MDI-prepolymer with polyether polyol using l,4-diazabicyclo[2.2.2]octane (DABCO) and dibutyktindilaurate as catalysts, silicone surfactant and water as foaming agent.
  • DABCO l,4-diazabicyclo[2.2.2]octane
  • dibutyktindilaurate as catalysts
  • silicone surfactant silicone surfactant
  • water foaming agent
  • DBDI is synthesized for low-flammable polyurethanes.
  • the synthetic method utilizes amidation of aryl bromide as a key step and the monomer was obtained in very good yields in large scale reaction batches (>20 g). Integration of DBDI into polyurethane structures affords ultra-fire-resistance as evidenced from the extremely low heat release rates and high char yields.
  • Polyurethane foams were also synthesized by employing BHDB-based oligomeric hydroxyl compound as part of polyol component that induced considerable char formation combined with a reduction of heat release capacity.
  • Avance400 spectrometer operating at the appropriate frequencies using residual solvent as internal reference. Infrared spectra were obtained on a Perkin Elmer Spectrum One FT-IR spectrometer equipped with an ATR accessory. HRMS-FAB data was acquired on a JEOL JMS 700 mass spectrometer. Molecular weights and polydispersity indices were measured by gel permeation chromatography (GPC) in DMF relative to polystyrene standards on systems equipped with two-column sets (Polymer Laboratories) and refractive-index detectors (HP 1047A) at 50 0 C with a flow rate of 0.75 mL/min.
  • GPC gel permeation chromatography
  • Flammability characteristics of the polymers such as heat release capacity was measured using pyrolysis combustion flow calorimetry (PCFC), where the average of three samples of 1-5 mg were pyrolyzed in nitrogen to 900 0 C at a rate of 1 °C/s, followed by complete combustion at 900 0 C.
  • Thermogravimetric analysis (TGA) was performed in nitrogen atmosphere on a DuPont TGA 2950 using a ramp rate of 10 °C/min.
  • Differential scanning calorimetry (DSC) measurements were performed on a DuPont Instrument DSC 2910 at a scan rate of 10 °C/min under a flow of nitrogen (50 mL/min). Glass transition temperatures (T g ) data were collected during the second heating from room temperature.
  • a Schlenk flask was thoroughly flame-dried under vacuum and then under nitrogen atmosphere (three cycles each). To this was added copper (I) iodide (4.14 g, 22 mmol), tribasic potassium phosphate (46.2 g, 220 mmol), and t-butyl carbamate (13.92 g, 119 mmol). These reagents were dried under vacuum and back-filled with nitrogen (three cycles). To this was added 4,4'-dibromobenzil, 1 (20 g, 54 mmol), N,N' -dimethyl ethyl enediamine (3.82 g (4.7 mL), 43 mmol) and anhydrous THF (100 mL).
  • FT-IR (cm 4 ): v 3371, 2977, 1705, 1682, 1605, 1525, 1502, 1409, 1392, 1368, 1319, 1235, 1121, 1155, 1057, 996, 904, 826, 772.
  • HRMS-FAB m/z M + calcd 426.2155; found 426.2136.
  • FT- IR (cm "1 ): v 3312, 2978, 2603, 2497, 2267, 1747, 1664, 1599, 1523, 1475, 1409, 1308, 1220, 1 180, 1 157, 1036, 993, 830, 761.
  • HRMS-FAB m/z M + calcd 278.0691 ; found 278.0684.
  • FT-IR (cm 4 ): v 3347, 2953, 1682, 1599, 1512, 1454, 1417, 1334, 1302, 1220, 1 172, 1043, 995, 912, 828, 772, 674.
  • HRMS-FAB m/z [M+l] + calcd 317.131 1 ; found 317.1391.
  • FT-IR (cm '1 ): v 3327, 2924, 2855, 1702, 1682, 1598, 1536, 1509, 1453, 1418, 1333, 1220,
  • BHDB-containing copolymers can be made by copolymerization of BHDB,
  • ASTM D 3801 Five specimens having weight and dimensions listed in Table
  • Dl were cut from the plaque and conditioned to temperature 23 C +1-2 C for 48 hours prior to testing and tested within 30 minutes of removal from chamber.
  • each specimen was suspended vertically from the clamped upper 6-mm of the specimen, with a distance of 300-mm from bottom edge of specimen to cotton surface, 100% cotton measuring 50 x 50 x 6-mm.
  • a blue, premixed methane-air flame measuring 20-mm in height was obtained using a Bunsen burner. The flame was applied to the center of the bottom edge of specimen, with the top of the burner held 10-mm from to the bottom edge of specimen. The burner flame orientation faces the front of the specimen (13-mm width) and is held at 45 degrees to the vertical direction allowing dripping.
  • ASTM D 5048 Because the specimens burned very little in the ASTM D
  • ASTM D 3801 test and due to the limited amount of material available, the ASTM D 3801 specimens were wiped with acetone and allowed to dry at room temperature and retested at the opposite end according to ASTM D 5048.
  • each specimen was suspended vertically from the clamped upper 6-mm of the specimen, with a distance of 300-mm from bottom edge of specimen to cotton surface, 100% cotton measuring 50 x 50 x 6-mm.
  • a blue flame measuring 125-mm high with a blue inner cone of 40-mm was obtained by mixing methane and air. The tip of the blue cone of the flame was applied to the bottom narrow edge of specimen.
  • the burner flame orientation faces the narrow (3mm width) edge of the specimen held by hand at 20 degrees to the vertical plane to allow dripping.
  • Burner maintains 20 degrees while maintaining the 40-mm distance. Burner was moved 150-mm away from specimen between 5 second impingements. The test method begins with specimen flame exposure for 5 seconds then immediately removing flame for 5 seconds, then repeating 4 additional times. After the exposure to the burner, the afterflame was recorded and the afterglow time was recorded. Table D3 shows the criteria for vertical classification according to ASTM D 5048.
  • FIG. Dl shows the test specimens after testing according to ASTM D 3801 testing (top) and ASTM D 5048 (bottom). Charring is limited to the portion of the specimen immersed in the flame during the test, as there was no visible flame spread after removal from the burner flame in either the ASTM D3801 or 5048 tests.
  • Table D4 contains the results of the ASTM D 3801 testing.
  • Table DS contains the UL 94 rating criteria for the test, showing that the BHDB/BPA polyarylate obtained a V-O rating.

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Abstract

La présente invention concerne de nouveaux polymères et matériaux ignifugeants, leur synthèse et leur utilisation. Plus particulièrement, les polymères ignifugeants sont des polymères dérivés de désoxybenzoïne.
PCT/US2009/038789 2008-03-31 2009-03-30 Polymères anti-inflammables dérivés de désoxybenzoïne WO2009123969A2 (fr)

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US14/859,336 US9822205B2 (en) 2008-03-31 2015-09-20 Deoxybenzoin-derived anti-flammable polymers
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WO2012008916A1 (fr) * 2010-07-14 2012-01-19 Agency For Science, Technology And Research Composé ininflammable et intumescent
US20140357829A1 (en) * 2013-05-17 2014-12-04 University Of Massachusetts Multifunctional deoxybenzoin-based monomers and resins having reduced flammability
US9080001B2 (en) 2011-05-02 2015-07-14 University Of Massachusetts Flame-retardant derivatives

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US10065913B2 (en) 2015-10-07 2018-09-04 The University Of Massachusetts Unsaturated deoxybenzoin compounds and polymers prepared therefrom
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